Shoe polishing compositions containing n,n - bis - (bis - amino - s - triazinyl)-alkylamines



United States Patent US. Cl. 1063 2 Claims ABSTRACT OF THE DISCLOSUREShoe polishing compositions contain certain new N,N- bis(bis-amino-s-triazinyl)-alkylamines which serve as polishing agents andwhich reduce the tendency of leather to absorb water. Compositionscontaining these new and other new N,N-bis(bis-amino-s-triazinyl)-alkylamines and certain tris-amino-s-triazinesand 1,4-bis[bis-amino-striazinyl]-piperazines are also useful for othersurface treating purposes, particularly as floor waxes and as textilesofteners.

This application is a division of our pending patent application, Ser.No. 560,855, filed June 27, 1966, now abandoned and is also acontinuation-in-part thereof.

This invention concerns certain newN,N-bis-(bisamino-s-triazinyl)-alkylamines which are useful as surfacetreating agents and are the principal components in shoe polishes.

By surface treating agents in the present description are meant agentswhich can be used for the protection and conservation, e.g. by coatingor waxing of surfaces of all types such as, for example, agents for thetreatment of surfaces of inorganic materials such as metal, stone, tile,etc., and of organic materials such as wood, leather, synthetic plastic(e.g. linoleum), textiles, paper etc.

More particularly, the surface treating agents according to thisinvention comprise, as principal constituent, striazine derivatives ofthe formula wherein A represents the group in which R represents a loweralkyl radical, namely an alkyl radical of from 1 to 5 carbon atoms, andR represents an alkyl radical having from to 18 carbon atoms,

B represents the group in which R and R have the meanings given above,the

pyrrolidino, piperidino, 4-lower alkyl-piperazino, morpholino, orhexamethyleneimino group, and

3,467,532 Patented Sept. 16, 1969 ice C represents the pyrrolidino,piperidino, 4-methyl-piperazino, morpholino or hexamethyleneiminoradical, or the grouping of the formula FI Y i (H) wherein each B hasthe meaning given above, and X is an alkylimino radical or thepiperazine-l,4-diyl radical, and, in those compounds falling underFormula I in which each of A and B represents the group C representsbesides the substituents defined above, also the group wherein each of Rand R independently of the other represents a substituted orunsubstituted alkyl radical having from 1 to 20 carbon atoms.

More in particular, the alkyl radicals symbolized by R and R, can besubstituted by halogen atoms such as fluorine, chlorine, or bromineatoms, or by hydroxyl groups. Preferably such substituted alkyl radicalshave not more than 5 carbon atoms. The alkyl radicals of the alkylarninogroup symbolized by X contains preferably from 1 to 5 carbon atoms.

The following classes of s-triazines are particularly valuable as maincomponents in the surface treating agents according to this invention.

(1) Compounds of the formula A-Qq-B;

wherein A has the same meaning as in Formula I,

B represents pyrrolidino, morpholino, piperidino, N- (loweralkyl)-piperazino or hexamethyleneimino, and C represents the samesubstituents as A, or as B or it represents the grouping (II) Compoundsof the formula B1 A v wherein A and C have the same meanings as inFormula III, B represents the same as A or as B in Formula III, and Rrepresents alkyl of from I to 5 carbon atoms.

(III) Compounds of the formula /N N\ it r m r in which A and C have thesame meanings as in Formula III.

Among the compounds falling under Formulas I11 and IV, a subclass ofcompounds which fall under the formulas hydroxy-lower alkyl N N Achloro-lower alkyl N wherein A and R have the same meanings as givenhereinbefore, are textile softening agents which impart relativelylittle or no water repellance to detergent-hardened textile materialssoftened therewith, e.g., to towels and the like goods in whichwater-repellency is not desirable. The compounds are preferably appliedfrom alcoholic, e.g., from isopropanol solution. Application fromglacial acetic acid solution is also possible but less desirable in viewof smell and acidity of such agents, even after dilution with water.

On the other hand, a preferred class of compounds according to theinvention, which falls under the for- AZF Im Y wherein A and B have thesame meaning as given hereinbefore, and

A \N /N A l P/ L N G: C: wherein A has the same meaning as givenhereinbefore, and C represents A or B are distinguished asgloss-imparting, self-polishing waxes which are particularly useful as aprincipal constituent of dry-bright polishing compositions.

fr Y Ni V wherein A and R have the same meanings as given hereinbefore,are waxes of brown or dark-brown to brownish black shade and serve aspolishing agents or principal constituents of such agents for polishingleather, e.g., shoe leather, especially also in order to retard thetendency of such leather to absorb water.

The waxes of the Formulas IX to XI, inclusive, given hereinbefore arereadily emulsifiable. When used in major amounts (e.g., 20 to 70% byweight calculated on the total weight of solids) in surface-treatingagents, especially in floor polishes, they impart to such polishes acertain gloss which is further enhanced by rubbing, e.g., with a softcloth or the like, or, especially in the case of compounds of Formula]X, in which B represents N-(lower alkyl)-piperazino, and in the case ofthe compounds of Formula X, supra, by subsequent washing of suchsurface, in particular floors, with water or with alkaline detergents.This constitutes an important progress, because many commerciallyavailable floor polishes will show enhanced gloss after rubbing with,e.g. a soft cloth or a polishing brush, but will not withstand washingwith water and especially not with alkaline agents.

In the compounds of Formula I, and especially in those of Formulas III,IV and V, the presence of at least one amino group having one shorterand one longer alkyl substituent as represented by A in those formulas,is necessary to obtain compounds suitable for use as main polishconstituent in surface treating agents according to the invention.

The trisamino-s-triazine derivatives of Formula I have well definedmelting points and wax-like properties; they can thus be used instead ofcommercial natural and synthetic waxes or together therewith for thetreatment and finishing of surfaces of all types. They have thecharacteristic properties of natural waxes such as solubility in fattysolvents, miscibility with natural and synthetic waxes and, with theaddition of suitable emulsifying agents, can be worked up in water toform finely dispersed emulsions. The new compounds produce coatingswhich are resistant to chemicals, particularly they have good stabilityto alkali. In their excellent suitability as waxes, they are equivalentfor all practical purposes to the montanic acid esters.

Surface-treating agents according to the invention are obtained bymixing a trisamino-s-triazine derivative of Formula I or several suchderivatives with the usual substances which are suitable for thetreatment of surfaces. Such substances are, for example, the following:natural and synthetic waxes, resins, silicones, etc. which improve thephysical properties, also solvents, as well as inorganic and organicfillers, e.g., silicates, milled plastics, anionic, cationic ornon-ionic dispersing agents, cleansing agents such as, e.g., natural andsynthetic soaps, tensioactive substances, pigments, agents to improvethe stability to light, stabilizers of all types such as corrosioninhibitors, scents, dyestuffs, biocidal active substances or agentscontaining such substances, e.g., insecticides, fungicides,bactericides, etc.

More particularly, the surface-treating agents according the theinvention, for instance in the form of floor polishes, can also contain,besides a compound or compounds of Formula I, as main component,volatile solvents such as are used in wood-sealing agents, namely, ethylacetate, acetone, lmethylethyl ketone, ethanol, toluene and the like.

The surface-treating agents according to the invention can be in theform of and used as aerosols, solvents, emulsions, semi-solid and solidpastes. The agents can thus serve to protect and to finish surfaces(e.g., polishing waxes) of all types, by which is also included thetreatment of paper, e.g., the production of carbon paper.

Trisamino-s-triazines of Formula I wherein two bisamino-s-triazineradicals are bound together by the piperazine-1,4-diyl radical are knowncompounds. They can be obtained by reacting two molecules of a2-halogen-4,6- bis-amino-s-triazine correspondingly substituted in theamino group with piperazine, the reaction being preformed attemperatures between 100 and 200 C., preferably in an inert gasatmosphere and optionally in the presence of an inert solvent and aproton acceptor.

The new tris-amino-s-triazines of the more restricted general formula NA( IE ('1' (XII) wherein A and B have the meanings given in Formula I,and C represents the pyrrolidino, piperidino, 4-methylpiperazino,morpholino or hexamethyleneimino radical or the group of the generalformula (XIII) wherein B has the meaning given in Formula I and X'represents an alkylimino radical, or when A and B represent the group Cmay also represent the group wherein each of R and R have the meaningsgiven in Formula I, are obtained according to the invention by reactingcyanuric chloride with (a) Two mols of the same or with one mol of eachof two different secondary amines containing the radicals R and Rdefined above and with one mol of a secondary amine containing theradicals R and R defined above,

(b) With two mols of the same or one mol of each of two differentsecondary amines containing the radicals R and R defined above and withone mol of pyrrolidine, piperidine, 4-methyl-piperazine, morpholine orhexamethyleneimine, or

(c) With one mol of a secondary amine containing the radicals R and Rdefined above and with 2 mols of pyrrolidine, piperidine,4-methylpiperazine, morpholine or hexalmethyleneimine or with one mol ofeach of two of the heterocyclic bases mentioned above, or

(d) With one mol of a secondary amine containing the radicals R and Rdefined above, one mol of pyrrolidine, piperidine, 4-methyl-piperazine,morpholine or hexamethyleneimine and with one mol of a secondary amineintroducing the group of general Formula X111 defined above, or

(e) With 2 mols of the same or one mol of each of two differentsecondary amines containing the radicals R and R defined above and withone mol of a secondary amine introducing the group of general FormulaXII-I defined above, the reaction optionally being performed in thepresence of a solvent or diluent and also a proton acceptor.

As solvent for the reaction of the first and second chlorine atom ofcyanuric chloride, those usual for this reaction are used such as water,mixtures of acetone and water, other mixtures of organic solvents withwater, halogen hydrocarbons and aromatic hydrocarbons. 1norganic basessuch as the carbonates and hydroxides of alkali metals, and organicbases such as secondary and tertiary amines are used as protonacceptors. The reaction temperature for the exchange of the firstchlorine atom is from -20 to |10 C., for the second chlorine atom from10 to and for the third chlorine atom from 100 to 200 C.

The following non-limitative examples describe surface finishing agentsaccording to the invention. Where not otherwise stated, parts andpercentages are given therein by weight. The abbreviations AN. and S .N.signify acid number and saponification number, respectively. Thetemperatures are given in degrees centigrade.

EXAMPLE 1 4.95 parts of1,4-bis-[2',4'-bis-N-methyl-N-n-octadecylamino-s-triazinyl- 6')-piperazine,

4.05 parts of petroleum wax (M.P. 86-88"; A.N. 13-16; S.N. 45-55;penetration 4-6 at 100 g./25/5 sec.), 0.63 part of the condensationproduct of oleyl alcohol and ethylene oxide (molar ratio about 1:5), asemulsifier, 0.54 part of olein, 0.54 part of aminomethyl propanol, 77.89parts of water.

1.20 parts of colophoniurn-modified phenolic resin having a meltingpoint of about 152, the phenolic resin base of which produced asdescribed in Example 2 of US. Patent 2,532,374,

0.40 part of cone. ammonia,

8.40 parts of water.

0.02 part of trimethyl-('y-perfluoro-octylamido-propylene)-ammoniumiodide, as wetting agent,

0.40 part of tris-(butoxethyl-phosphate),

0.98 part of water.

The components of the mixture (a), with the exception of water, aremelted at the homogeneous melt is cooled to 100110 and then slowlyadded, while stirring strongly, to the boiling water. The emulsionformed is cooled to room temperature and first the mixture (b) and thenmixture (c) are added while stirring.

The resultant gloss-imparting emulsion wax composi tion is excellentlysuitable for the care of modern floors, polyvinyl chloride tiles beinggiven a polish value of 27.7 measured on a 45 glossmeter of the Langetype (100 being the gloss of a black mirror viewed under an angle of 45As a comparison an emulsion produced according to the above example inwhich the abovementioned piperazine derivative according to theinvention was replaced by carnauba wax only attained a polish value of117.7. In addition, the wax emulsion produced according to the aboveexample with the substance according to the invention is considerablyless slippery than one produced with carnauba wax.

The s-triazine derivative which is a main component of theabove-described surface-treating composition, is of the structuralformula and is produced as follows:

37 parts of 2,4,6-trichloro-s-triazine are dissolved in 400 parts ofanhydrous toluene and, at room temperature, a solution of 120 parts ofN,N-dimethyl-N-n-octadecylamine in 400 parts of anhydrous toluene isadded dropwise. The whole is then refluxed under an atmosphere ofnitrogen until the calculated amount of chloromethane has been splitoff. The solvent is then distilled ofl in vacuo. A-fterrecrystallization from acetone, the 2-chloro-4,6-1)is-N-methyl-N-n-octadecylamino-s-triazine melts at 58-62".

34 parts of 2-chloro-4,6-bis-N-methyl-N-n-octadecylamino-s-triazine and10 parts of piperazine are heated for 5 hours at 110-115 under anatmosphere of nitrogen. After cooling, excess piperazine and piperazinehydrochloride which have been formed are removed by washing with waterand the residue is dried. 1,4-bis-[2,4-bis- N methyl N n octadecyl aminos triazinyl- (6)]-piperazine is obtained. After recrystallization fromdioxan it melts at 98-102.

EXAMPLE 2 2.24 parts of1,4-bis-[2-morpholino-4'-methyl-N-n-octadecylamino-s-triazinyl- 6')]-piperazine, 1.68 parts of carnauba wax, 1.68 parts of ester wax(montanic acid ester, M.P.

80-83; A.N. 20-30; S.N. 135-150), 0.44 part of the same emulsifier asused in Example 1, 0.40 part of olein, 0.40 part of aminomethylpropanol, 33.16 parts of water.

16.70 parts of an aqueous dispersion of polystyrene (emulsion polymer)having a solids content of about 36% by weight,

0.10 part of the condensation product of nonylphenol and ethylene oxide(molar ratio about 1:15),

23.20 parts of water.

3.00 parts of alkali-soluble pentaerythritol resinate po1y ester resinhaving a melting range of 169-181 and an acid number of 190-200", aslevelling agent,

1.00 part of cone. ammonia,

16.00 parts of water.

The components of the mixture (a), with the exception of the water, aremelted at 150", the homogeneous melt is cooled to 100-110 and thenadded, while stirring strongly, to the boiling water. The emulsionformed is cooled to room temperature and the mixtures (b) and (c) areadded one after the other while stirring.

The resultant dry-bright wax-polymer emulsion is excellently suited forthe care of modern floors in that the coating itself possess a certaingloss which can, however, be increased by polishing to a value of 24.3.

The s-triazine derivative, which is used as a main component in theabove-described surface-treating composition, is produced as follows.

185 parts of cyanuric chloride are dissolved in 1000 parts of carbontetrachloride and 87. 1 parts of morpholine are added while stirringintensively at 0 to 5". A solution of 54 parts of sodium carbonate in300 parts of water is then said. After stirring for 2 hours, a solutionof 290 parts of N-methyl-N-n-octadecylamine in 1000 parts of carbontetrachloride is added dropwise at 10 to 15 and then a solution of 54parts of sodium carbonate in 300 parts of water is added dropwise. Thewhole is then slowly heated and afterwards refluxed for 5 hours. Oncompletion of the reaction, the solvent is distilled oil. The residue isstirred with 1500 parts of acetone. The undissolved part is filtered011? under suction, thoroughly washed with water and dried. 2-chloro-4-morpholino-6-N-methy1-N-n-octadecylamino-s-triazine is obtained which,after recrystallization from alcohol, melts at 52-54".

482 parts of2-chloro-4-morpholino-6-N-methyl-N-noctadecylamino-s-triazine and partsof piperazine are dissolved in 4000 parts of warm xylene and 45 parts ofpulverized sodium hydroxide are added. The whole is then refluxed usinga water separator under an atmosphere of nitrogen. On completion of thewater separation, the mixture is refluxed for another 3 hours. Thereaction mixture is filtered hot, the filtrate is evaporated to drynessin vacuo and the residue is stirred with 4000 parts of acetone. Thesolid, undissolved part is separated, thoroughly washed with water anddried in vacuo. 1,4-bis[2'- morpholino 4' Nmethyl-N-n-octadecylamino-s-triazinyl- (6)]-piperazine is obtainedwhich, after recrystallization from acetic acid ethyl ester, melts at108-112.

EXAMPLE 3 2.250 parts of the same colophoniu m-modified phenolic resinas used in Example 1,

0.675 part of cone. ammonia,

12.075 parts of water.

The components of the mixture (a), with the exception of the water, aremelted at the homogeneous melt is cooled to 100-110 and then slowlyadded, while stirring, to the boiling water. The emulsion formed iscooled to room temperature and the mixture (b) is added while stirring.

The resultant dry-bright emulsion wax is excellently suitable for thecare of modern floors; it is self-polishing, but its gloss can still beincreased by subsequent rubbing with a soft cloth. If this coatingobtained on polyvinyl chloride tiles is washed with a moist cloth thenthe gloss value rises from 29 to 35 whilst, as a comparison, the glossvalue of an emulsion produced according to the above example in whichthe wax body according to the invention is replaced by carnau-ba waxonly rises on Washing from 29.5 to 30.5.

A similar composition is obtained when replacing the triazinyl componentin the above composition by an equiv alent amount of2-morpholino-4,6-bis-(N-methyl-N-noctadecylamino) s triazine or ofN,N-bis-[2,4-di-(N'- methyl Nn-octadecylamino)-s-triazinyl-(6)]-N-ethylamine.-

The s-triazine derivatives used in the above compositions are producedas follows:

(1) 48.2 parts of 6-chloro-2-(N-methyl-N-n-octadecyl-:amino)-4-morpholino-s-triazine and 49.2 parts of 6'ethylamino2-N-methyl-N-n-octadecylamino-4-morpholino-striazine are dissolved byheating in 400 parts by volume of anhydrous pyridine while stirring. Thereaction mixture is then refluxed for 18 hours under an atmosphere ofnitrogen whereupon it is filtered hot, the filtrate is concentrated todryness in vacuo and the residue thoroughly washed with water and driedin vacuo. N,N-bis[2-N'- methyl Nn-octadecylamino-4-morpholino-s-triazinyl- (6)]-N-ethyl-amine isobtained which, after recrystallization from acetone, melts at 76-78".

(2) 37 parts of cyanuric chloride are dissolved in 400 parts ofanhydrous toluene and, at room temperature, a solution of 120 parts ofN,N-dimethyl-N-n-octadecylamine in 400 parts of anhydrous toluene isadded dropwise. The whole is then refluxed under an atmosphere ofnitrogen until the calculated amount of chloromethane has been splitoff. The solvent is then distilled off in vacuo. After recrystallizationfrom acetone, the 2-chloro-4,6-bis-N-methyl-N-n-octadecylamino-s-triazine melts at 58-62.

34 parts of 2-chloro-4,6-bis-N-methyl-N-n-octadecylamino-s-triazine and10 parts of morpholine are heated for hours at 110-115 under anatmosphere of nitrogen. After cooling, excess morpholine and morpholinehydrochloride which have been formed are removed by washing with waterand the residue is dried. 2morpholino-4,6-bis- (N methylN-n-octadecylamino)-s-triazine is obtained, which afterrecrystallization from methyl alcohol melts at 80-82.

(3) 67.8 parts of2-chloro-4,6-bis-N-methyl-N-n-octadecyl-amino-s-triazine and 68.7 partsof 2-ethylamino-4,6- bis-N-methyl-N-n-octadecylamino-s-triazine aredissolved by heating in 400 parts by volume of anhydrous pyridine whilestirring. The reaction mixture is then refluxed for 18 hours under anatmosphere of nitrogen whereupon it is filtered hot, the filtrate isconcentrated to dryness in vacuo and the residue thoroughly washed withwater and dried in vacuo. N,N bis [2,4 di-(N'methylN-n-octadecylamino) striazin-(6)-yl]-N-ethylan1ine is obtained which, after recrystallizationfrom acetone, melts at 55- 57. When this brownish-black substance isincorporated in a surface-treating agent of the composition given inExample 3, in lieu of the tri-substituted ethylamine component, andblack boot leather is polished therewith, it is given a black glosssimilar to that of a standard black boot polish, and a retarded tendencyto absorb water.

EXAMPLE '4 5.0 parts of 2-(N-methyl-piperazino)-4-morpholino-6- (N"methyl-N"-n-octadecyl-amino)-s-triazine are dissolved in 95.0 parts ofisopropanol, if necessary while heating, whereupon a clear solution isformed. This solution is excellently suitable for softening textilesparticularly cotton towelling which has become hardened by repeatedwashing. Such goods are laid for a few minutes in a bath which contains40 parts of the above-mentioned solution per 1000 parts by volume ofwater. After treatment in this bath, the goods are wrung out and driedin the air. Even greatly hardened and scratchy cotton towelling regainsits original soft and fleecy handle. It is not rendered unduly waterrepellant by such treatment.

Similar good softened dispersions are produced as described in Example4, supra, by replacing the 40 parts of isopropanolic 5%-softenersolution used therein by the same amount of an isopropanolic 5%-solutionof N,N- bis [2,4di-(N-methyl-N'-n-octadecyl-amino)-s-triazinyl-(6)]N-ethylamine, or by 4parts of an isopropanolic 5% solution of2,4-di-(N-methyl-N-n-octadecyl-amino)- 6 [N (18hydroxyethyl)-N-(ti-chloroethyl)-amino]-striazine. M.P. 8082.

The textile softener compound used in Example 4, supra, is produced asfollows:

185 parts of cyanuric chloride are dissolved in 1000 parts of carbontetrachloride and 87.1 parts of morpholine are added while stirringintensively at 0 to 5. A solution of 54 parts of sodium carbonate in 300parts of water is then added. After stirring for 2 hours, a solution of290 parts of N-methyl-N-n-octadecylamine in 1000 parts of carbontetrachloride is added dropwise at 10 to 15 and then a solution of 54parts of sodium carbonate in 300 parts of water is added dropwise. Thewhole is then slowly heated and afterwards refluxed for 5 hours. Oncompletion of the reaction, the solvent is distilled off. The residue isstirred with 1500 parts of acetone. The undissolved part is filtered offunder suction, throughly Washed with water and dried.2-chloro-4-morpholino-6- N-methyl-N-n-octadecylamino-s-triazine isobtained which, after recrystallization from alcohol, melts at 5254.

482 parts of2-chloro-4-morpholino-6-N-methyl-N-noctadecylamino-s-triazine and 110parts of N-methylpiperizine are dissolved in 4000 parts of warm xyleneand 45 parts of pulverized sodium hydroxide are added. The whole is thenrefluxed in a water separator under an atmosphere of nitrogen. Oncompletion of the water separation, the mixture is refluxed for another3 hours. The reaction mixture is filtered hot, the filtrate isevaporated to dryness in vacuo and the residue is stirred with 4000parts of acetone. The solid, undissolved part is separated, throughlywashed with water and dried in vacuo. 2-N'- methylpiperazine 4morpholino-6-N"-methyl-N"-n-octadecylamino-s-triazine is obtained which,after recrystallisation from dioxan melts at 48-51 EXAMPLE 5 (Dry-brightemulsion wax) 3.19 parts of 2,4-bis-(N-methyl-N-n-octadecyl-amino)-6-(N-methyl-piperazino -s-triazine, 3.19 parts of paraffin (M.P. 50-52),6.38 parts of montanic acid ester wax (M.P. -83;

A.N. 20 30; S.N. 135-150 1.70 parts of olein, 1.36 parts of aminomethylpropanol, 1.53 parts of cetyl alcohol polyglycol ether with 4 to 5ethyleneoxy groups, as emulsifying agent, 67.66 parts of water.

2.25 parts of the same colophonium-modified phenolic resin as used inExample 1,

0.67 part of aqueous concentrated ammonia (25%) and 12.07 parts ofwater.

The components of mixture (a), with the exception of the water, aremelted at 150 and stirred until a homogeneous melt is obtained. The meltis cooled to 100-110, the water is brought to the boil and is then addedthereto, and the resulting mixture (a) is cooled to room temperature.This mixture (a) is obtained in the form of an emulsion to which thesolution (b) is added. The resultant emulsion is excellently suitablefor the care of modern floors, such as vinyl flooring.

EXAMPLE 6 10 parts of 2,4-bis-(N-methyl-N-n-octadecyl-amino)-6-pyrrolidino-s-triazine were dissolved in parts of isopropanol byheating to 90 on the water bath.

Leather samples were impregnated with this solution by immersion thereinfor 5 minutes, and then air-dried. The leather then contained about 13%of the aforesaid s-triazine, calculated on the dry weight of theleather.

The impregnated leather samples were then immersed for several hours inwater together with untreated control samples of the same leather. Whileuntreated leather absorbed water very rapidly, e.g. (calculated on theweight of the dry leather) within the first hour, and a total of in 18hours, the impregnated leather samples 1 1 1 2 absorbed water much moreslowly. Thus the amount of EXAMPLE 8 water absorbed reached 100% onlyafter 18 hours.

EXAMPLE 7 (a) (a) 4.200 parts of 1,4-bis[2,4'-bis-N-methyl-n-octadecyl-5 amino-s-triazinyl-(6) ]-piperazine, 4.480 parts ofN,N'-bis-[2-morpholino-4-N-methyl-n-oc- 1.355 parts of montanic acidester wax (M.P. 80-83";

tadecylamino-s-triazinyl-(6)]-piperazine, A.N. 20-30; S.N. 135-150),3.360 parts of an isocyanate polymeric wax (softening 4.200 parts of thesame isocyanate polymeric wax as used point 93, A.N. 25-35; S.N. 50-65;penetration 1-3 at in Example 7, 100 5 see), as described inManufacturing 0 0.735 parts of montanic acid wax (M.P. 80-83; A.N.Chemist and Aerosol News, July 1965, p. 59, 140-155; SN, 160-180), 2,300Parts Of mofltaflic acid fister Wax 0.630 part of the same emulsifyingagent as used in A.N. 20-30; S.N. 135-150), Example 1, 0.560 part ofmontanic acid ester Wax (M.P. 80-83"; 0210 part of KOH 10%,

A.N. 140-155; S.N. 160-180), 0.630 part of aminomethyl propanol, 0.448part of the same emulsifier as used in Example 1, 62.04 parts of water.0.560 part of aminomethyl propanol, 0.224 part of a saturated aqueoussolution of KOH, 66.568 parts of water. 3.50 parts of the samecolophonium-modified phenolic (b) resin as used in Example 1, 2.80 partsof the same colophonium-modified phonolic b g g sg ggi i ammoma resin asused in Example 1, p e 1.00 part of concentrated ammonia, (0) 1620 Partsof Water 0.10 part of a condensation product of nonylphenyl and cethylene oxide (molar ratio about 1:15), 0.01 part of the same wettingagent as used in Example 1, 0.90 part of water. 0.99 part of water. Th hth h e components of t e mixture a wi t e exceptlon compound: Sa 1 the35 2 5; of water, are melted at 150, the homogeneous melt is 0 water areme f a 6 Omog neolls cooled to 100-l10 and then slowly added, whilestirring cooled to 100-110 and then slowly added, wh1le stirringStrongly to the boiling water The emulsion formed is Strongly to thebmhng Water The emulslon formed 15 cooled to room temperature and firstthe mixture (b) and cooled to 9 temperature and {mxture (b) then mixture(0) are added while stirring i. thenl mufmre gg zii iggg g g g 23563 g:The resulting gloss-imparting emulsion wax composition i g 3 forgthecare of modemp floors M 0 r e is excellently suitable for the care ofmodern floors. When cc y Su d d subjecting vinyl asbestos plates to atreatment with the 'g' liiz i s c l u fo i a ii n iig eafci i th e abcid es ii gd Composition according to Example 8 on the one hand, and witha similar com osition in which the triazine derivative g q h Whlch l g g2 Comp 1%? g? g 40 has been replaced by an equal amount of montanic acidy a at composltlon m w m owever I? ester wax second com onent of theabove com sition mOrPh9hnWi'N'P1ethy1'mOctadecylamme S wallingon the other hand, and testing the slip resistan of th: (6)]'plperazme 1Sreplai-zed by an Fqual amount of t e differently treated plates in thesame manner as dethird of the above-mentioned constituents, namely mon-E 1 7 th d f 8 6 tanic acid ester wax of M.P. 80-83 A.N. 20-30 and sen mxzimp e en ynamlc 3 1p re.slstanceo S N 135 150 lbs. is found in thecase of plates treated with the composition according to Example 8 ascompared with a value of When vinyl asbestos plates are polished withthe cornposition according to Example 7, on the one hand, and ggg g g im the case of the mazme denvatlve free with the last-mentionedconventional triazine derivative- Floors negated with the composition ofExample 8 thus S igggi g g 3 gz gg g z g ggg gf g combine high gloss,which is even enhanced after washing Method No. 30 of Standard Methodsof Testing Paint, g m f g f detergents an unexpectedly Varnish, Lacquerand Related Products, published as g p DEF 1053 by the British Ministryof Defence, then, the EXAMPLE 9 composition according to the inventionshows a value of While the convantlonal composltlon compared Similarsurface-treating compositions according to fl} Shows a Y of 1 3 theinvention are produced by replacing the triazine com- If $1ml1a dynamlcP l'eslstance Values shown by ponent in each of the compositions of thepreceding ex- 1115 aforesafd composltlon of EXamPIe 7 are amples by anequivalent amount of an s-triazine of the tained also in the case of theconventional composltlon, a Formula I in which A, B, and C represent theSubstituconsiderable amount of adjuvant such as finely dispersed entgroups shown in the respective column f h f lsilica would have to beadded, but would lead to a strong lowing tabl reduction of gloss in thepolished surface. Floors treated The s-triazine derivatives are producedby the methods with the composition according to the invention thereforeexemplified hereinbefore using equivalent amounts of combine high glosswith pronounced slip-resistance. correspondingly substituted startingmaterials.

TABLE Example No. A B C M.P., C

CH: CH:

(1) -N\ N\ N 66-67 CmHu (3181131 /CH3 /CH| (2) -N\ N\ -N 68-70 C18H37CzsHzr TABLE-Continued Example No. A B 0 My" 0 C CH: CH: (3) N\ -N\ --NN-CH1 63-65 gl Hu 111111 E 2 (4) N -N --N O 90.9

CmHn

CH3 CH1 CaH40H (5) N\ -N\ N 78-80 C4Ho C4H9 C3H4OH (6) -N -N -N 1111 11CnHu C|H1 l CH: N /CH! (1 -N\ -1 o -N l-N\ 76-78 nHu H5 1 L CnHu CH;CaHn (8) -N\ -N -N CmHar CuaHzr CuHa: CmHn C;H7 CaH7 (10) -N\ --N\ -NN--CH:

C2115 /C2 11) N -N CmHa; Cm aa 012 CmHfl CH3 05H CzH4OH 1a -N -N -N Cmas 10H21 C2H4OH 0 H C4H9 CQHQOH (14) -N\ 012 2: 012 25 CsHoOH CaH1 03H!C(HaOH 15 -N N N 010 21 10 CIHBOH C Hq CZHB CIBHU (16) --N N N 011 11 1811 C2 4OH 01H; /CH3 CzH4OH (17) -N Cu u u as 021E401 /CH$ 05H CZHAOH(18) -N 111115 CnHzs CzH1Br (19) N\ N N 19- 20 TABLE'Contlnued ExampleNo. A B c M.P., 0

M N N N-OgH| -N N N NC,H; (41) L uHu J r-NC1|HJ1 CH: CHOH CH 42 N -N i iNf I--N nHu C:H40H N L, nHn

N (C:H|OH)| C C H /C4H| 4H|OH /N a (43) N T mHn 411101! N N 1011::

N(CIHIOH)I 0 H /C:H|OH V N 951111 4) TR CuHn aHaBr L, nHn

wherein each of R and R represents alkyl of iron: 1"

:to 5 carbon atoms, and R, represents alkyl of from 10 to 18 carbonatoms, in

an amount sufiicient to impart gloss to footwear 5 polished therewithand further comprising a polish .hase in the form of an emulsion. a

2. A shoe polish as defined in claim 1, wherein said compound isN,N-bis[2,4-bis-(N-rnethyl-N- -octadecylamino) -s-triazinyl- 6)]-N-ethylamine.

References Cited UNITED STATES PATENTS 3,108,029 10/1963 Wohnsiedleretal. 3,374,235 3/1968 Varsanyi et a1. 106-3 XR 3,277,065 10/1966Petropoulos et al.

FOREIGN PATENTS 576,016 5/1959 Canada.

JOAN B. EVANS, Primary Examiner JULIUS FRQME, Assistant Examiner US. Cl.X.R.

